Assuring precision and calibration linearity in ultrasensitive suppressed ion chromatography by using deliberately contaminated hydroxide eluent.

EXPERIMENTAL: and theoretical studies were conducted to investigate low and non-linear responses in sub-micro molar-level suppressed ion chromatography with a hydroxide eluent. A calculated response was derived using experimentally determined detector effluent ion composition data and compared with measured experimental responses. The calibration curve was non-linear, and its slope varied considerably with different instrumental setups and operating conditions. The non-linearity of the solution conductivity response was determined by two acid-base equilibria of water and carbonic acid, and fluoride ion. By using eluent contaminated with para-toluene sulfonate at micro molar level, the non-linear response was greatly alleviated.

Sorption-desorption of Sb(III) in different soils: Kinetics and effects of the selective removal of hydroxides, organic matter, and humic substances.

To examine the Sb(III) retention by three soils with different properties (Ferrosol, Primosol and Isohumosol), kinetic batch experiments were carried out for Sb(III) adsorption-desorption, followed by Sb release using a sequential extraction procedure. In addition, hydroxides, organic matter, and humic substances were selectively removed by washing the soil with oxalate, sodium dithionate-citrate-bicarbonate, H2O2, and NaOH. The effects of removing these substances on Sb(III) retention were investigated by comparing the Sb distribution coefficients and desorption rates. The results indicated that exogenous Sb(III) was adsorbed onto all three soils rapidly at first and then more slowly. After 168 h of adsorption, most of the adsorbed Sb(III) was irreversibly retained in stable fractions by the Ferrosol. Oxidation reactions negatively affected Sb(III) retention by the Primosol and Isohumosol, and a large proportion of the Sb adsorbed remained mobilizable. The oxalate washing markedly enhanced Sb retention but the sodium dithionate-citrate-bicarbonate washing decreased Sb retention in all three soils. The H2O2 and NaOH washings affected Sb retention by the Ferrosol more than Sb retention by the Primosol and Isohumosol. Changes in the pH and hydroxides caused by the washing strongly affected Sb sorption-desorption. The results improve our understanding of the mobility and bioavailability of exogenous Sb(III) in soils and might benefit future remediation option of Sb-contaminated soils.

A rapid, accurate and sensitive method with the new stable isotopic tags based on microwave-assisted dispersive liquid-liquid microextraction and its application to the determination of hydroxyl UV filters in environmental water samples.

A rapid, accurate and sensitive method, using the stable isotope labeling (SIL), microwave-assisted dispersive liquid-liquid micro extraction (MADLLME) and the ultra-high performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS), was developed and validated for the determination of hydroxyl UV Filters in environmental water samples. A pair of new isotopic tags D0-/D3-1-methylindole-3-acetic acid (D0-/D3-MIAA) is synthesized, with which a simple yet efficient pretreatment MADLLME-SIL is developed. Under the optimized conditions (80℃, 240W, 180s), the sample pretreatment including analyte extraction, pre-concentration and isotope labeling can be finished conveniently in only 9min. D0-/D3-MIAA labeling improves the chromatographic retention by strengthening the hydrophobicity and enhances the MS response for 3-4 orders of magnitude. Excellent linearity is established by the H/D ratios of 1/10-10/1 with the correlation coefficients >0.9990. The quite low detection limits (0.54-1.79ng/L) are achieved, ensuring the trace detection. This method is successfully applied to a series of environmental water samples. The recoveries (93.2%~103.5%) are significantly improved and the analysis time is largely reduced (<15min). The excellent sensitivity, accuracy, recovery, and efficiency demonstrate this MADLLME-SIL-LC-MS/MS method a superior alternative for the analysis of UV filters in water samples.

A combined upflow anaerobic sludge bed, aerobic, and anoxic fixed-bed reactor system for removing tetramethylammonium hydroxide and nitrogen from light-emitting diode wastewater.

A laboratory study using a combined upflow anaerobic sludge bed (UASB) and aerobic and anoxic fixed-bed reactor system was undertaken to explore its capability for removing tetramethylammonium hydroxide (TMAH) and nitrogen from light-emitting diode wastewater. When the organic loading rate was maintained at 0.26-0.65 kg TMAH m(-3 )d(-1), the UASB reactor removed 70-100% of TMAH through methanogenesis. When the [Formula: see text] -N loading rate was maintained at 0.73-1.4 kg [Formula: see text]-N m(-3 )d(-1), the aerobic reactor oxidized 31-59% of [Formula: see text]-N to [Formula: see text]-N through nitritation. When the nitrogen loading rate was maintained at 0.42-0.75 kg N m(-3 )d(-1), the anoxic reactor removed 27-63% of nitrogen through anammox. The performance data of the combined reactor system agreed well with the stoichiometric relationships of methanogenesis, nitritation, and anammox. The batch studies showed that a higher initial TMAH concentration of up to 2520 mg L(-1) gave a higher methanogenic activity of up to 16 mL CH4 g(-1) VSS d(-1). An increase in the initial TMAH concentration of up to 500 mg L(-1) gradually decreased the activity of ammonia-oxidizing bacteria; whereas an increase in the initial TMAH concentration of up to 47 mg L(-1) imposed a marked inhibiting effect on the activity of anammox bacteria.

Electrocatalysis and electroanalysis of nickel, its oxides, hydroxides and oxyhydroxides toward small molecules.

The electrocatalysis toward small molecules, especially small organic compounds, is of importance in a variety of areas. Nickel based materials such as nickel, its oxides, hydroxides as well as oxyhydroxides exhibit excellent electrocatalysis performances toward many small molecules, which are widely used for fuel cells, energy storage, organic synthesis, wastewater treatment, and electrochemical sensors for pharmaceutical, medical, food or environmental analysis. Their electrocatalytic mechanisms are proposed from three aspects such as Ni(OH)2/NiOOH mediated electrolysis, direct electrocatalysis of Ni(OH)2 or NiOOH. Under exposure to air or aqueous solution, two distinct layers form on the Ni surface with a Ni hydroxide layer at the air-oxide interface and an oxide layer between the metal substrate and the outer hydroxide layer. The transformation from nickel or its oxides to hydroxides or oxyhydroxides could be further speeded up in the strong alkaline solution under the cyclic scanning at relatively high positive potential. The redox transition between Ni(OH)2 and NiOOH is also contributed to the electrocatalytic oxidation of Ni and its oxides toward small molecules in alkaline media. In addition, nickel based materials or nanomaterials, their preparations and applications are also overviewed here.

Sorption coefficients and molecular mechanisms of Pu, U, Np, Am and Tc to Fe (hydr)oxides: a review.

Pu, U, Np, Am and Tc are among the major risk drivers at nuclear waste management facilities throughout the world. Furthermore, uranium mining and milling operations have generated an enormous legacy of radioactively contaminated soils and groundwater. The sorption process of radionulcides onto ubiquitous Fe (hydr)oxides (FHOs; hematite, magnetite, goethite and ferrihydrite) is one of the most vital geochemical processes controlling the transport and fate of radionuclides and nuclear wastes in the subsurface zones. Meanwhile, understanding molecular-level chemical speciation of radionuclides onto FHOs is crucial to model their behavior in subsurface environments, and to develop new technologies for nuclear waste treatment and long-term remediation strategies for contaminated soils and groundwater. This review article aims (1) to provide risk or performance assessment modelers with macroscopic distribution coefficient (K(d)) data of Pu, U, Np, Am and Tc onto FHOs under different conditions (pH, radionuclide concentration, solution ion strength, sorbent loading, partial pressure of CO(2) (P CO(2)), equilibrium time) pertinent to environmental and engineered systems, and (2) to provide a microscopic or molecular-level understanding of the chemical speciation and sorption processes of these radionuclides to FHOs.

Determination of the hydrate structure of an isolated alcoholic OH in hydrophobic medium by infrared and near-infrared spectroscopy.

This paper reports the structure of the hydrate complex of an isolated alcoholic OH, produced in a small amount in hydrophobic solution in heptane. The structure was determined from the changes, caused by hydration, in the infrared and near-infrared spectra of 2-nonanol in the solution. The changes were exhibited in the "difference" spectrum, in which the spectrum of the solution before hydration was subtracted from that after hydration. The difference spectrum showed a "plus" or "minus" peak at the frequency of the stretching band of a free OH, depending on whether the concentration was below or above about 2%(v/v), respectively. The plus peak appears because the OH stretching band of the isolated OH that acts as an acceptor does not change in frequency but significantly increases in intensity, in agreement with theoretical calculations. In contrast, the stretching band of an isolated OH that acts as a donor shifts downward. This shift decreases the intensity at the stretching frequency of a free OH, giving rise to a minus peak at the frequency in the difference spectrum. It was concluded that an isolated OH is hydrated in the manner as HO...HOH and OH...OH(2) at a concentration below and above about 2%, respectively, in the hydrophobic solution of 2-nonanol.

Coextraction during reactive extraction of phenylalanine using Aliquat 336: modeling extraction equilibrium.

Reactive liquid-liquid extraction can be used to recover hydrophilic fermentation products that would not otherwise partition into nonpolar solvents through an ion-exchange reaction at the two-phase interface. However, the ion-exchange reagent may not be specific to the solute of interest and other compounds present may also be extracted. In this study, the effect on solute extraction of other compounds present in the extraction medium was investigated for phenylalanine extraction using Aliquat 336. The extent of extraction at equilibrium was modeled using the equilibrium constants for the reactions present in the process. The interaction of different species within a multicomponent medium was examined using the model and experimental results. It was found that the extent of extraction and coextraction is controlled by the thermodynamics of each extraction reaction and, due to the formation of a common product, the interaction between each of the reactions. The main competition to reactive extraction will come from hydrophobic anionic compounds that will be present in fermentation broth.

Fabrication and properties of spray-dried nanofeatured spherical Ni(OH)2 materials.

Spherical agglomerates of nanostructured beta-phase Ni(OH)2 with the general formula Ni1-xCox(OH)2 (x = 0, 0.1, 0.3) for use as cathode materials were produced by a modified method including coprecipitation of Ni or Ni composite hydroxide and further spray drying of the precipitated and washed slurry. This process leads to the formation of spherical agglomerate particles with a narrow Gaussian-type distribution range. The method permits faster and cheaper production of cathode materials with a higher specific surface area and similar or better capacity and cycle life compared with the materials prepared via conventional technology.

Ethyl acetate extraction of spin-trapped free radicals: a reevaluation.

We have suggested the use of ethyl acetate for extraction of hydroxyl or superoxide radical adducts of the spin trap phenyl N-tert-butyl nitrone (PBM). The technique produced EPR spectra with narrow line widths, the radical adducts were more stable, and there were sufficiently large differences between the isotropic nitrogen hyperfine coupling constant (alpha N) and the beta hydrogen coupling constant (alpha H beta) for both the hydroxyl and superoxide radical adducts to allow their simultaneous quantitation in mixtures. However, Kalyanaraman, Mottley, and Mason have suggested that our assignments of alpha N and alpha H beta were incorrect and that extraction of spin-trapped adducts into ethyl acetate is not as useful as we had proposed. This paper demonstrates that their objections are unfounded and are based on a computational error that they made when they attempted to calculate the hyperfine splittings in their spectra.

Anionic sites of human erythrocyte membranes. I. Effects of trypsin, phospholipase C, and pH on the topography of bound positively charged colloidal particles.

The effects of pH, trypsin, and phospholipase C on the topographic distribution of acidic anionic residues on human erythrocytes was investigated using colloidal iron hydroxide labeling of mounted, fixed ghost membranes. After glutaraldehyde fixation at pH 6.5-7.5, the positively charged colloidal particles were bound to the membranes in small randomly distributed clusters. The clusters of anionic sites were reversibly aggregated by incubation at pH 5.5 before fixation at the same pH. These results correlate with the distribution of intramembranous particles found by Pinto da Silva (J. Cell Biol.53:777), with the exception that the distribution of anionic sites on a majority of the fixed ghosts at pH 4.5 was aggregated instead of dispersed. The randomly distributed clusters could be nonreversibly aggregated by trypsin or phospholipase C treatment of intact ghosts before glutaraldehyde fixation. Previous glutaraldehyde fixation prevented trypsin and pH induced aggregation of the colloidal iron sites. Evidence that N-acetylneuraminic acid groups are the principal acidic residues binding colloidal iron was the elimination of greater than 85% of the colloidal iron labeling to neuraminidase-treated cell membranes. Colloidal iron binding N-acetylneuraminic acid residues may reside on membrane molecules such as glycophorin, a sialoglycoprotein which contains the majority of the N-acetylneuraminic acid found on the human erythrocyte membrane.